Polyvinyl acetal resin sheets containing o-cresyl toluene sulphonate



' l6 produce compositions which can b rolled, the case of polyvinylacetalclehyde acetal resins.

UNITED STATES PATENT OFFICE POLYVINYL ACETAL RESIN SHEETS CON- gAIhgNGO-CRESYL TOLUENE SULPHO- Henry B. Smith, Rochester, N. Y., asslgnor toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NoDrawing. Application December 15, 1937, Serial No. 180,032

3 Claims. (Cl. 26036) This nven ion relates to plastic compositions, ormore parts of the solvent or solvent mixture and more particularly tocompositions comprising being sed p 100 Parts Of the reSin- From apolyvinyl acetal resin and a conditioning agent. a out 2 '60 100 Partmore Of e-eresyl ue e One objectof thisinvention is to producecomsulphonate p 100 Parts Of resin y e e positions of matter which maybe made into per- D y d, depending upon the nature of the resin 5manently transparent, strong and flexible sheets and the purpose Whichthe Sheets are to be or films of desired thinness which are substanusduita l proportions f sy tol n tially waterproof, are unaffected byordinary u p e for any resin and y P p ay be photographic fluids andpossess the desired propreadily determined y D the erties of a supportfor sensitive photographic manu actu e of shee s e o p o raphiccoatings. Another object of my invention is to film base, from 2 to 25Parts Of y toluene produce compositions of tt hi can b sulphonate per100 parts of resin are suitable in made into sheets suitable for use inlaminated, th ease of P y yl butyralde y acetal shatter-proof glass.Still another object is to d from 2 t 50 parts per 00 pa ts f r s n intruded, molded or otherwise Worked into relae es Solution is east as aSheet, o ve tively thick sheets and massive lastics. A furevap rated,andstripp d m ast n surface.

ther object is to produce compositions suitable Sheets for use inlaminated glass y be for use in lacquers, artificial silk filaments,wrap- 'm by c sting, or may be made without the ping tissues and thelike. Other objects will use of t e so by extrusion, for mple 20hereinafter appear. in the manner set forth in application SeriahNo.

I have discovered that o-cresyl toluene sul- 147,934 of John S? Kimbleand Ernest phonate is a very useful conditioning agent for Blalekhard,fi d June 12, 1937- instance, polyvinyl acetal resins. I may useo-cresyl p- 45 or more parts of o-cresyl toluene sultoluene sulphonate,or I may use a mixture of D e a d 100 P s Of DOlyvlhyl butyralde- 25o-cresyl p-toluene sulphonate and o-cresyl ,my acetal res n y be ed atroom p toluene sulphonate. Not only does o-cresyl tolull e Or at a ducedtemperature, in a Suitene sulphonate serve as a plasticizer in theacable mixer, d t mixture may 1iheh be Worked cepted sense of the term,increasing the flexon hot rolls, in h manner described in ibility andtoughness of polyvinyl acetal resin a e 2,048,636 COhkllh, until 30films, sheets, or other objects or masses contain- Plete hOmOgeniZatiOna taken p a e. mass ing it, but when used in amounts of about 45 thus prduced may then be xtrud d through parts or more per 100 parts of certainof th an annular die, and the tube so formed slit to polyvinyl acetalresins, namely the polyvinyl o-Cresyl toluene sulphonate at iS acetalresins in which a predominating propore t for a Polyvinyl acetal 35 tionof the acetal groups are butyraldehyde acetal he p y y a e S can beprepared by groups, it has an unusual and remarkable effect reacting p yy alcohol t an aldehyde in which I may call elasticizing. That is tosay, the pres f a acetal d sati n st, a sheet of a polyvinyl butraldehyde acetal resin e. g. a mineral a These resins can also becontaining about or more parts of o-cresyl p epared by Simultaneouslyde-estelifying a 40 toluene sulphonate per 100 parts of resin pospolyvny aliphatic ester and reacting the sesses the property which, in therubber industry, estellfiea io P d c With an aldehyde in the is known asnerve: namely, the property of presence of a de-esterify'ing catalystand acetal stretching to a considerable extent when tension condensationcatalyst. Mineral acids are cat- 45 is exerted upon it, and returning toits original alysts for both de-esterification and acetal for- 45dimensions when the tension is released. This mation. Among thepolyvinyl acetal resins with property renders such sheets, which I shall'call which o-cresyl'toluene sulphonate is useful may "rubbery sheets,particularly useful in the be mentioned, as illustrative examples, thepolymanufacture of shatter-proof glass. vinyl formaldehyde acetalresins, the polyvinyl For the manufacture of cast films or sheets,acetaldehyde acetal resins, the polyvinyl formal- 50 the polyvinylacetal resin and o-cresyl toluene dehyde acetaldehyde mixed acetalresins, the sulphonate may be dissolved in a suitable solvent polyvinylbutyraldehyde acetal resins, and the or solvent mixture, such, forinstance, as acetone, polyvinyl butyraldehyde acetaldehyde mixedmethanol, acetone-methanol mixtures, ethylene acetal'resins.

chloride-methanolmixtures, etc., about 300 to 500 Examples of thepreparation of polyvinyl 55 formaldehyde acetal resins may be found inU. 1 S. Patent 1,955,068, Examples 1, 4 and 5; in U. l 5 S. Patent2,036,092, Examples 1, 2, 3, 7 and 8; 1

3 in British Patent 454,691, Examples 1, 2, 3, 4,

5 i 5, 6 and 7; in British Patent 404,279, Example 3; 3 i and in BritishPatent 436,072, Examples 1, 2, 3, 4, 5, 6 and 7. Further examples of theprepara- 1 5 tion of polyvinyl formaldehyde acetal resins are 3 asfollows: 10 l :benzene was 45 centipoises, was dissolved in 75 lbs. of70% acetic acid. To this solution were 1 added 56 grams of hydroxylaminehydrochloride, 1

for stabilizing the resin, 5.25 lbs.. of trioxymethjylene, and 6.25 lbs.of HCl.

iwater, washed, and dried. Analysis showed the 3 resin to have anacetate group content equivalent ito 10.6% by weight of polyvinylacetate and a weight of polyvinyl alcohol.

ent No. 2,146,735. 70 lbs.- of polyvinyl acetate, the viscosity of whosemolar solution in benzene was 45 centi- ;poises, was dissolved in amixture of 336 lbs. of I Theresm, when analyzed, gave/a hydroxyl groupcontent equivalent to about 6.4 percent by weight 1 of polyvinylalcohol, an acetate group content tion of 318 grams of sodium nitrite in500 cc. of j equivalent about percent by w gm lwater, for stabilizingthe resin, 15.2 lbs. of tri- The j ireaction mixture was allowed tostand for 5 days 1 content equivalent to about percent by glacial aceticacid and 224 lbs. of water. After asolutior. was effected, there wereadded a solujoxymethylene and 17.5 lbs. of 35% HCl.

lat 40 C., whereupon 5 lbs. additional 35% HCl ;was added and thereaction continued for 6 days 40 longer: a total of 11 days at 40 C. Thereacjof aceticacid and 'ethyl alcohol, and the resin {was precipitatedby pouring into cold water,

,washed, and dried. Analysis showed the resin acetaldehyde acetaL jtohave an acetate group content equivalent to 10.7% by weight of polyvinylacetate and a weight of polyvinyl alcohol. The stabilization jofpolyvinyl acetal resins by nitrous acid is {claimed in the applicationof Charles R. Fordyce iand Martti Salo, Serial No. 159,193, filed August514, 1937, now Patent No. 2,159,263.

, Examples of the preparation of polyvinyl acetgaldehyde acetal resinsmay be found in U. S.

Patent 2,044,730, Example 1; U. S. Patent 1,955,

1068, Example 2; U. S. Patent 2,036,092, Examples 14, 5 and 6; BritishPatent 466,598, Examples 1, i 3, 4 and 7; British Patent 404,279,Examples 3 4, 5, 6, 7 and.8; U. S. Patent 1,990,399; and

French Patent 808,578, Examples 1, 2 and 3.

1 An additional example of the preparation of a jpolyvinyl acetaldehydeacetal resin is as follows: 100 lbs. of polyvinyl acetate, the viscosityof whose molar solution in benzene was 45 centilpoises, was dissolved in300 lbs. of ethyl alcohol. To this solution were added 30 lbs. ofparaldehyde and 25 lbs. of 35% HQ]. "The reaction mixture was allowed tostand for 4 days at 40 0,, after which it was diluted with ethyl 70alcohol, and the resin precipitated by pouring into cold water, washedand dried. Analysis showed the resin to have an acetate group contentequivalent to 2.1% by weight of polyvinyl acetate and a hydroxyl groupcontent equivalent 7 to 12.9% by weight of polyvinyl alcohol.

25 lbs. of polyvinyl acetate, the viscosity of ,whose molar solution(86.08 g. per liter) in follows:

The reaction lmixture was allowed to stand for 5 days at 40 3C., afterwhich it was diluted with acetic acid. 5 jThe resin was precipitated bypouring into cold 5 and the mixture precipitated into water.

Examples of the preparation of polyvinyl formaldehyde acetaldehyde mixedacetal resins may be found in British Patent 430,136, Examples 1, 2, 3,4, 5 and 6; British Patent 445,565, Example 2; British Patent 465,873,Examples 1, 2, 3, 4, 5 and 6; French Patent 808,586, Examples 1, 2, 3,4, 5, 6, 12, 13, 14, 15, 16, 17, 18 and 19.

Additional examples of the preparation of polyvinyl formaldehydeacetaldehyde mixed acetal res ns are given in the application of Ralph11. Talbot, Serial No. 85,960, filed June 18, 1936, as

"Example 1 parts (1.16 mol. calculated as monomeric vinyl acetate) 'of apolyvinyl. acetate (45 centipoises), 100 parts of ethyl alcohol, partsof ethyl acetate, 34 parts (.77 mol. as monomeric acetaldehyde) ofparacetaldehyde and 5.8 parts (.196 mol. as monomeric formaldehyde) ofparaformaldehyde were placed in an enamelled vessel and brought intosolution by stirring. When solution was complete, 10 parts of sulphuricacid (sp. g. 1.84) in 10 parts of water were added, and the mixturestirred. The mixture was maintained at a temperature of 40 C. for 144hours. The contents of the vessel were then diluted with about two and ahalf volumes of acetone, The precipitated resin was washed free fromimpurities by repeated changes of cold water, and dried.

polyvinyl acetate, a formaldehyde aceta group weight of polyvinylformaldehyde acetal and an acetaldehyde acetal group content equivalentto 5 about 73.9 percent by weight of polyvinyl acet- ;tion mixture wasthen diluted with a mixture j aldehyde acetal The polyvinyl acetalportion of the resin was therefore made up of about 19.7 percent bymoles of polyvinyl formaldehyde acetal and about 80.3 percent by molesof polyvinyl The resin was soluble 'in acetone to an extent whichpermitted coating 9.

'jhydroxyl group content equivalent to 11.2% by I film or Sheet from theresin "Example 2 50 parts (.58 mol. as monomer) of polyvinyl I acetate(45 centipoises), 50 parts of ethyl alcohol, 90 parts of ethyl acetate,17 parts (.385 mol.

as monomer) of paracetaldehyde, 2.9 parts (.098

mol. as monomer) of par'aformaldehyde, 5 parts 1 of sulphuric acid and 5parts of water were treated as in Example 1 for 161 hours. The wellwashed and dried resin gave upon analysis a hydroxyl group contentequivalent to about 9.6% 1 by weight of polyvinyl alcohol an acetategroup 3 content equivalent to about 4.1% by weight of polyvinyl acetate,a formaldehyde acetal group content equivalent to, about 13.9 percent byweight of polyvinyl formaldehyde acetal, and an The polyvinyl acetalportion of the resin I Example 3 1300 parts (15.1 mol. as monomer) of apoly yinyl acetate (45 centipoises) 1700 parts of ethyl acetate, 2250parts of ethyl alcohol (95%) and 48 parts (1.57 mol. as monomer) ofparaformaldehyde (trioxymethylene) 'were placed. in a 1.84) dissolved in51.5 parts of water were added,

and the whole was heated at about 70 C. for about five hours, agitatingthroughout. At this point, 266.4 parts (6.05 mol, as monomer) ofparacetaldehyde were added and heating at about 70- C. with agitationwas continued for a further period of twenty hours. The contents of thereaction vessel were neutralized with ammonium hydroxide anddiluted withwater precipitating the resin as a cake. The cake was cut into smallpieces and repeatedly washed with hot water until the resin was freefrom solvents, salts and other impurities. The resin, upon analysis,showed a hydroxyl group content equivalent'to about 10.1 percent byweight of polyvinyl alcohol, an acetate group content equivalent toabout 3.2 percent by weight of polyvinyl acetate, the

remainder of the weight of the resin being pbiyvinyl acetal. Thepolyvinyl acetal portion of the resin was made up of about 80 percent bymoles of polyvinyl acetaldehyde acetal and about 20 percent by moles ofpolyvinyl formaldehyde acetal. The resin was not quite soluble inacetone, but could be made to dissolve by admixing small amounts ofother solvents, such as alcohols, with the acetone.

Examples of the preparation of polyvinyl buiyraldehyde acetal resins maybe found in U. S. Patent 2,044,730, Examples 2, and 6; British Patent466,598, Example 5; French Patent 813,- 303, Example 1; French Patent813,514, Examples 1, 2, 3 and 4; and British Patent 459,878, Examples 1,2, 5, 6, 7, 8, 9 and 10.

Additional examples of the preparation of polyvinyl butyraldehyde acetalresins are as follows:

20 lbs. of polyvinyl acetate the viscosity of whose molar solution inbenzene was 45 centipulses, was dissolved in 20 lbs. of 95% ethylalcohol and 36 lbs. of ethyl acetate. To this solution was added 13 lbs.of butyraldehyde and a solution of 2 lbs. of sulphuric acid in 2 lbs. ofwater. The reaction mixture was allowed to stand for 8 days at 40 C.,after which it was diluted with acetone, and the resin precipitated bypouring" into cold water, washed anddried. Analysis showed the resin tohave an acetate group content equivalent to 7.8% by weight of polyvinylacetate and a hydroxyl group content equivalent to 4.8% by weight ofpolyvinyl alcohol.

23.6 lbs. of polyvinyl acetate, the viscosity of whose molar solution inbenzene was 45 centipoises, was dissolved in 56.5 lbs. of 95% ethylalcohol. To this solution was added 7.9 lbs. of butyraldehyde and 5.9lbs. of 35% I- ICl. The reaction mixture was allowed to stand for 4 daysat 40 C., after which it was diluted with ethyl alcohol and acetic acid,and the resin precipitated by pouring into cold water, washed, anddried. Analysis showed the resin to have an acetate group contentequivalent to 3.1% by weight of polyvinyl acetate and a hydroxyl groupcontent equivalent to 16.3% by weight of polyvinyl alcohol.

An example of the preparation of a polyvinyl butyraldehyde acetaldehydemixed acetal resin is givenin French Patent 813,303, Example 2.

What I claim as my invention and desire to be secured by Letters Patentof the United States l. A transparent, rubbery sheet comprising 100parts of a polyvinyl acetal resin in which a predominating proportion ofthe acetal groups are butyraldehyde acetal' groups, and at least 45parts, approximately, of o-cresyl toluene sulphonate as an elasticizertherefor.

2. A transparent, rubbery sheet comprising 100 parts of a polyvinylbutyraldehyde acetal resin and at least 45 parts, approximately, ofo-cresyl toluene sulphonate as an elasticizer therefor.

3. A transparent, rubbery sheet comprising a polyvinyl acetal resin inwhich a predominating proportion of the acetal groups are butyraldehydeacetal groups, and an amount of o-cresyl toluene sulphonate sufilcientto impart to the sheet a rubbery character without substantiallyimpairing its transparency.

HENRY B. SMITH.

